TW201641495A - Novel sulfur compound and composition for optical materials containing same - Google Patents

Abstract

According to one preferred embodiment of the present invention, a composition for optical materials, which contains a compound represented by formula (1) and a compound represented by formula (2), is able to be provided. This composition for optical materials enables stable storage of a compound represented by formula (2) at low cost, and also enables stable storage thereof with respect to temperature change. In addition, this composition for optical materials enables the achievement of an optical material which has good light resistance. (In formula (1), m represents an integer of 0-4; and n represents an integer of 0-2.) (In formula (2), m represents an integer of 0-4; and n represents an integer of 0-2).

Description

Novel sulfur compound and composition for optical material containing the same

The present invention relates to a novel sulfur compound and a composition for an optical material comprising the same, relating to an optical material suitable for use in a plastic lens, a ray, an optical fiber, a data recording substrate, a filter, etc., particularly a plastic lens. A novel sulfur compound and a composition for an optical material comprising the same.

Plastic lenses are lighter and more tough, and dyeing is easier. The properties required for plastic lenses are low specific gravity, high transparency, and low yellowness, and have high refractive index, high Abbe number, high heat resistance, and high strength as optical properties. The high refractive index can be used as the flaking of the lens, and the high Abbe number reduces the chromatic aberration of the lens.

In recent years, for the purpose of high refractive index and high Abbe number, many examples have been reported in which an organic compound having a sulfur atom is used. Among them, a polyepoxysulfur compound having a sulfur atom is known to have a good balance between a refractive index and an Abbe number (Patent Document 1). Further, since the polyepoxide compound can react with various compounds, a composition of various compounds is proposed in order to enhance physical properties (Patent Documents 2 to 5).

However, since the episulfide compound is difficult to store for a long period of time due to the high degree of reactivity, there is a proposal to refrigerate and store it (Patent Document 6) or a method of adding an epoxy compound having a halogen atom group (Patent Document 7).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 09-110979

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-298287

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-002783

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2001-131257

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2002-122701

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-327677

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2005-272418

However, in order to improve the refrigerating storage, it is necessary to have a dedicated cold storage, and the cost of the halogen resin is improved, and the epoxy compound having a halogen atom group is improved to have a disadvantage of the deterioration of the light resistance from the halogen. Furthermore, it is also required to be safely stored even when the temperature changes.

In view of the above-described conventional problems, an object of the present invention is to provide a composition for an optical material which can stably and inexpensively store a polymerizable compound such as an episulfide compound, and can be stably stored even when temperature changes, and can be obtained. An optical material with good light resistance.

The inventors of the present invention have found that the above problems can be solved by the following invention as a result of intensive research in such a situation. That is, the present invention is as follows.

<1> an episulfide compound represented by the following formula (1), (where m represents an integer from 0 to 4, and n represents an integer from 0 to 2).

<2> A composition for an optical material comprising the episulfide compound of the above <1> and a polymerizable compound other than the compound.

<3> The composition for an optical material according to the above <2>, wherein the content of the episulfide compound is 0.001 to 5.0% by mass.

<4> The composition for an optical material according to the above <2> or <3>, wherein the polymerizable compound is contained in an amount of from 95.0 to 99.999% by mass.

The composition for an optical material according to any one of the above-mentioned <2>, wherein the compound represented by the following formula (2) is contained as the polymerizable compound. (where m represents an integer from 0 to 4, and n represents an integer from 0 to 2).

<6> The composition for an optical material according to the above <5>, which contains 40 to 99.999 mass% of the compound represented by the above formula (2).

The polymer composition for optical materials according to any one of the above <2> to <6>, and the total amount of the composition for the optical material is 0.0001% by mass. 10% by mass of a polymerization catalyst.

<8> An optical material composition according to any one of the above <2> to <6> or a polymerizable curable composition according to <7> above.

<9> An optical lens comprising the optical material as described in <8> above.

<10> A method for producing an optical material, which comprises adding a polymerization catalyst of 0.0001% by mass to 10% by mass based on the total amount of the composition for an optical material according to any one of the above <2> to <6>. Then, the step of polymerization hardening is carried out.

According to the present invention, it is possible to manufacture a composition for an optical material which is stable and easy to manufacture when manufacturing an optical material having a high refractive index It is preferable to store a polymerizable compound such as an episulfide compound, and it is possible to stably store the temperature even when the temperature changes, and to obtain an optical material having good light resistance.

[Formation of the Invention]

The present invention will be described in detail below.

The present invention is a compound represented by the above formula (1) and a composition for an optical material, which comprises a compound represented by the above formula (1) and a polymerizable compound other than the compound represented by the above formula (1). Examples of the polymerizable compound other than the compound represented by the above formula (1) include an episulfide compound, a vinyl compound, a methacrylic compound, an acrylic compound, and a propylene compound, but an episulfide compound is preferred, and the above is more preferred. a compound represented by the formula (2).

In the composition for an optical material of the present invention, the ratio of the compound represented by the above formula (1) is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 3.0% by mass, particularly preferably 0.01 to 1.0% by mass. When the amount of the compound represented by the above formula (1) is less than 0.001% by mass, a sufficient effect may not be obtained, and when it exceeds 5.0% by mass, heat resistance may be lowered.

Further, in the composition for an optical material of the present invention, the ratio of the polymerizable compound is preferably from 95.0 to 99.999 mass%, more preferably from 97.0 to 99.995 mass%, particularly preferably from 99.0 to 99.99 mass%. When a compound represented by the above formula (2) is used as the polymerizable compound, the composition for an optical material is used. The ratio of the compound represented by the above formula (2) is preferably from 40 to 99.999 mass%, more preferably from 50 to 99.995 mass%, particularly preferably from 60 to 99.99 mass%.

Hereinafter, the compound represented by the above formula (1) and the compound represented by the above formula (2) will be described in detail.

The present invention is a compound represented by the above formula (1), and the compound represented by the formula (1) is used in the composition for an optical material of the present invention. In the formula (1), m is preferably an integer of 0 to 2, n is an integer of 0 or 1, more preferably m is 0 and n is 1, or n is 0, and preferably n is 0. Compound. The compound represented by the formula (1) may be used singly or in combination of two or more kinds.

Hereinafter, a method for producing the compound represented by the formula (1) of the present invention will be described, but the production method is not particularly limited.

The method for producing the compound represented by the formula (1) of the present invention can be obtained by reacting a compound represented by the formula (2) obtained by a known method with acetic acid. Hereinafter, a method of producing a compound represented by the formula (1) from the compound represented by the formula (2) will be described.

The compound represented by the formula (2) is reacted with acetic acid or acetic anhydride to obtain a compound represented by the formula (1). Preferred is acetic acid. The acetic acid or acetic anhydride is the same molar number as the compound represented by the formula (2), that is, the theoretical amount, but if the reaction speed and purity are emphasized, the theoretical amount to the theoretical amount is 20 times the molar amount. Preferably, it is 1.5 times the theoretical amount, 10 times the theoretical amount, more preferably 2 times the theoretical amount, and 10 times the theoretical amount. Further, it is preferred to use a solvent. As long as the solvent is capable of dissolving acetic acid or acetic anhydride, The compound represented by the formula (1) and the compound represented by the formula (2) are not particularly limited, and specific examples thereof include ethers such as diethyl ether and tetrahydrofuran, and acesulfame-K. Hydroxyl ethers such as sulphonic acid, butyl sulphate, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene. Preferred are ethers, aromatic hydrocarbons, and halogenated hydrocarbons, and more preferred are aromatic hydrocarbons and halogenated hydrocarbons. These solvents are used singly or in combination.

The reaction temperature is not particularly limited as long as it can carry out the reaction, but it is usually carried out at 10 ° C to 50 ° C. When the temperature is less than 10 ° C, the reaction rate is lowered, and the reaction does not proceed sufficiently. When the temperature exceeds 50 ° C, the formation of the polymer is remarkable.

The reaction time is not particularly limited as long as it can carry out the reaction, and is usually carried out for 10 minutes to 50 hours, preferably 30 minutes to 30 hours, more preferably 30 minutes to 20 hours. When the temperature is less than 10 minutes, the reaction does not proceed sufficiently, and when it exceeds 50 hours, the formation of a polymer is remarkable.

The reaction pressure is not particularly limited as long as it can carry out the reaction, and it can be carried out under reduced pressure under pressure, and it is usually carried out under normal pressure.

In the composition for an optical material of the present invention, as the polymerizable compound, a compound represented by the above formula (2) can be preferably used. Specific examples of the compound represented by the formula (2) include bis(β-epithiopropyl) sulfide, bis(β-epithiopropyl) disulfide, and bis(β-epoxypropylsulfide). Methane, 1,2-bis(β-epithiopropylthio)ethane, 1,3-bis(β-epithiopropylthio)propane, 1,4-bis(β-cyclothiopropane An episulfide compound such as thio)butane. The compound represented by formula (2) is It can be used alone or in combination of two or more types.

Among them, preferred compounds are bis(β-epithiopropyl) sulfide (n=0 in the formula (2)) and bis(β-epithiopropyl) disulfide (m=0 in the formula (2), n = 1), the most preferred compound is bis(β-epithiopropyl) sulfide (n = 0 in the formula (2)).

The composition for an optical material of the present invention may further comprise a polythiol compound as a polymerizable compound in order to improve the color tone of the obtained resin upon heating. When the total amount of the composition for an optical material is 100% by mass, the content of the polythiol compound is usually 1 to 25% by mass, preferably 2 to 25% by mass, particularly preferably 5 to 20% by mass. When the content of the polythiol compound is less than 1% by mass, yellow discoloration may occur during lens molding, and when it exceeds 25% by mass, heat resistance may be lowered. In the present invention, the polythiol compound to be used may be used singly or in combination of two or more kinds.

Specific examples thereof include methane dithiol, methane trithiol, 1,2-ethanedithiol, 1,2-dihydrothiopropane, 1,3-dihydrothiopropane, and 2,2-di. Hydrogen thiopropane, 1,4-dihydrothiobutane, 1,6-dihydrothiohexane, bis(2-hydrothioethyl)ether, bis(2-hydrothioethyl) sulfide, 1,2 - bis(2-hydrothioethyloxy)ethane, 1,2-bis(2-hydrothioethylthio)ethane, 2,3-dihydrothio-1-propanol, 1,3 -dihydrothio-2-propanol, 1,2,3-trihydrothiopropane, 2-hydrothiomethyl-1,3-dihydrothiopropane, 2-hydrothiomethyl-1,4 - dihydrothiobutane, 2-(2-hydrothioethylthio)-1,3-dihydrothiopropane, 4-hydrothiomethyl-1,8-dihydrothio-3,6- Dithiooctane, 2,4-dihydrothiomethyl-1,5-dihydrothio-3-thiapentane, 4,8-dihydrothiomethyl-1,11-dihydrogen 3-,6,9-thiaundecane, 4,7-dihydrothiomethyl-1,11-dihydrothio- 3,6,9-thiaundecane, 5,7-dihydrothiomethyl-1,11-dihydrothio-3,6,9-thiaundecane, 1,1,1- Hydrazine (hydrothiomethyl)propane, hydrazine (hydrothiomethyl)methane, ethylene glycol bis(2-hydrothioacetate), ethylene glycol bis(3-hydrothiopropionate), Diethylene glycol bis(2-hydrothioacetate), diethylene glycol bis(3-hydrothiopropionate), 1,4-butanediol bis(2-hydrothioacetate) , 1,4-butanediol bis(3-hydrothiopropionate), trimethylolpropane thioethylene glycol ester, trimethylolpropane thiophanate propionate, pentaerythritol decyl glycol ester , pentaerythritol guanidinium hydrogenthiopropionate, 1,2-dihydrothiocyclohexene, 1,3-dihydrothiocyclohexene, 1,4-dihydrothiocyclohexene, 1,3- Bis(hydrothiomethyl)cyclohexene, 1,4-bis(hydrothiomethyl)cyclohexene, 2,5-dihydrothiomethyl-1,4-dithiocyclohexane, 2 , 5-dihydrothiomethyl-1,4-dithiocyclohexane, 2,5-bis(2-hydrothioethylthiomethyl)-1,4-dithiocyclohexane, 2, 5-dihydrothiomethyl-1-thiocyclohexane, 2,5-dihydrothioethyl-1-thiocyclohexane, 2,5-dihydrothiomethylthiophene, 1,2-di Hydrogenthiobenzene, 1,3-dihydrothiobenzene, 1,4-dihydrogen Benzobenzene, 1,3-bis(hydrothiomethyl)benzene, 1,4-bis(hydrothiomethyl)benzene, 2,2'-dihydrothiobiphenyl, 4,4'-dihydrogen Thiophenylbiphenyl, bis(4-hydrothiophenyl)methane, 2,2-bis(4-hydrothiophenyl)propane, bis(4-hydrothiophenyl)ether, bis(4-hydrogen) Thiophenyl) sulfide, bis(4-hydrothiophenyl)anthracene, bis(4-hydrothiomethylphenyl)methane, 2,2-bis(4-hydrothiomethylphenyl) Propane, bis(4-hydrothiomethylphenyl)ether, bis(4-hydrothiomethylphenyl) sulfide, 2,5-dihydrothio-1,3,4-thiadiazole, 3,4-thiophene dithiol, 1,1,3,3-indole (hydrothiomethylthio)propane.

Among these, preferred specific examples are bis(2-hydrothioethyl) sulfide, 2,5-dihydrothiomethyl-1,4-dithiocyclohexane, and 1,3-bis(hydrogen). Thiomethyl)benzene, 1,4-bis(hydrothiomethyl)benzene, 4-hydrothiomethyl-1,8-dihydrothio-3,6-dithiooctane, 4,8 -Dihydrothiomethyl-1,11-dihydrothio-3,6,9-thiaundecane, 4,7-dihydrothiomethyl-1,11-dihydrothio-3 ,6,9-thiaundecane, 5,7-dihydrothiomethyl-1,11-dihydrothio-3,6,9-thiaundecane, 1,1,3,3 - hydrazine (hydrothiomethylthio) propane, pentaerythritol guanidinium hydrogenthiopropionate, pentaerythritol decyl glycol ester, trimethylolpropane thioethylene glycol ester), trimethylolpropane thiophanate Propionate, more preferably bis(2-hydrothioethyl) sulfide, 2,5-bis(2-hydrothiomethyl)-1,4-dithiocyclohexane, 4-hydrogenthio group Methyl-1,8-dihydrothio-3,6-dithiooctane, 1,3-bis(hydrothiomethyl)benzene, pentaerythritol guanidinothiopropionate, pentaerythritol decyl glycolate Particularly preferred compounds are bis(2-hydrothioethyl) sulfide, 2,5-dihydrothiomethyl-1,4-dithiocyclohexane, 4-hydrothiomethyl-1,8- Dihydrothio-3,6-dithiooctane

The composition for an optical material of the present invention may further comprise a polyisocyanate compound as a polymerizable compound in order to improve the strength of the obtained resin. When the total amount of the composition for an optical material is 100% by mass, the content of the polyisocyanate compound is usually 1 to 25% by mass, preferably 2 to 25% by mass, particularly preferably 5 to 20% by mass. When the content of the polyisocyanate compound is less than 1% by mass, the strength may be lowered, and if it exceeds 25% by mass, the color tone may be lowered. The polyisocyanate compound used in the present invention may be used alone or in combination of two or more kinds.

As such a specific example, diethylene diisocyanate and tetramethylene can be mentioned. Diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexene diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexene, 1,4-bis(isocyanate methyl) Cyclohexene, isophorone diisocyanate, 2,6-bis(isocyanatemethyl)decalin, isocyanuric acid triisocyanate, methylphenyl diisocyanate, o-tolidine diisocyanate, diphenylmethane Isocyanate, diphenyl ether diisocyanate, 3-(2'-isocyanatocyclohexyl)propyl isocyanate, isopropylidene bis(cyclohexyl isocyanate), 2,2'-bis(4-isocyanatophenyl) Propane, triphenylmethane triisocyanate, bis(diisocyanato)phenyl, methane 4,4',4"-triisocyanate-2,5-dimethoxyaniline, 3,3'-dimethoxy Benzidine-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diisocyanate biphenyl, 4,4'-diisocyanate group- 3,3'-Dimethylbiphenyl, dicyclohexylmethane-4,4'-diisocyanate, 1,1'-methylenebis(4-isocyanatobenzene), 1,1'-Asia Methyl bis(3-methyl-4-isocyanate), m-extension Isocyanate, p-extended decyl diisocyanate, m-tetramethyl decyl diisocyanate, p-tetramethyl decyl diisocyanate, 1,3-bis(2-isocyanate-2-propyl)benzene, 2,6-bis(isocyanatemethyl)naphthalene, 1,5-naphthalene diisocyanate, bis(isocyanatemethyl)tetrahydrodicyclopentadiene, bis(isocyanatemethyl)dicyclopentadiene, bis(isocyanate A) Tetrahydrothiophene, bis(isocyanatemethyl)nordecene, bis(isocyanatemethyl)adamantane, thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiododecyl diisocyanate, double [(4-Isocyanatemethyl)phenyl]sulfide, 2,5-diisocyanate-1,4-dithiocyclohexane, 2,5-diisocyanate methyl-1,4-dithiocyclohexane 2,5-diisocyanate Thiophene, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate.

However, the polyisocyanate compound which can be used in the present invention is not limited thereto, and these may be used alone or in combination of two or more.

Among these, preferred specific examples are isophorone diisocyanate, methylphenyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, m-extended diisocyanate, p-extension base II. Isocyanate, m-tetramethyl decyl diisocyanate, p-tetramethyl decyl diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexene, 1,4-bis(isocyanatomethyl) Cyclohexene, bis(isocyanatemethyl)nordecene, and 2,5-diisocyanate methyl-1,4-dithiocyclohexane. More preferably, the compound is isophorone diisocyanate or methylphenylene Isocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexene, m-extended decyl diisocyanate, particularly preferred compound is isophorone diisocyanate, m- Streptylene diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexene.

Further, with respect to the NCO group of the polyisocyanate compound, the ratio of the SH group in the polythiol compound, that is, the number of SH groups of the polythiol compound/the number of NCO groups of the polyisocyanate compound (SH group/NCO group) is preferably 1.0 to 2.5, more preferably 1.25 to 2.25, particularly preferably 1.5 to 2.0. When the ratio is less than 1.0, yellow color may be formed during lens molding, and if it exceeds 2.5, heat resistance may be lowered.

In order to enhance the income of the composition for an optical material of the present invention The refractive index of the resin may also include sulfur as a polymerizable compound. When the total amount of the components for the optical material is 100% by mass, the content of the sulfur is usually 0.1 to 15% by mass, preferably 0.2 to 10% by mass, particularly preferably 0.3 to 5% by mass.

The shape of the sulfur used in the present invention may be any shape. Specifically, the sulfur is fine powder sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimed sulfur, etc., and is preferably finely divided fine powder sulfur.

The method for producing sulfur used in the present invention is any method. The sulfur production method includes a sublimation purification method from a natural sulfur ore, a sulfur recovery method in which a sulfur buried in the ground is excavated by a melting method, a hydrogen sulfide obtained by a desulfurization step such as oil or natural gas, and the like, and any method can be used.

The particle size of sulfur used in the present invention is smaller than that of 10 mesh, that is, sulfur is preferably finer than fine mesh of 10 mesh. When the particle size of sulfur is larger than 10 mesh, sulfur is more difficult to completely dissolve. Therefore, in the first step, a poor reaction or the like is caused, and a problem may occur. The particle size of sulfur is preferably smaller than 30 mesh, and is smaller than 60 mesh.

The purity of sulfur used in the present invention is preferably 98% or more, more preferably 99.0% or more, still more preferably 99.5% or more, and most preferably 99.9% or more. When the purity of sulfur is 98% or more, the color tone of the obtained optical material is further improved as compared with less than 98%.

When the optical material composition of the present invention is polymerized and cured to obtain an optical material, it is preferred to add a polymerization catalyst. The composition of the present invention can be a polymer curable composition containing a composition for an optical material and a polymerization catalyst. As a polymerization catalyst, there are amine, phosphine, or phosphonium salts, especially hydrazine. The salt is preferably a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary sulfonium salt, and a secondary sulfonium salt, and is a quaternary ammonium salt having good compatibility with a composition for an optical material and a quaternary phosphonium salt. The salt is more preferred, and the fourth grade bismuth salt is even better. As a more preferable polymerization catalyst, there are mentioned tetra-n-butylammonium bromide, triethylbenzylammonium chloride, hexadecyldimethylammonium chloride, and 1-n-dodecylpyridinium chloride. A quaternary phosphonium salt such as a quaternary ammonium salt, tetra-n-butylphosphonium bromide or tetraphenylphosphonium bromide. Among these, a more preferred polymerization catalyst is tetra-n-butylammonium bromide, triethylbenzylammonium chloride, and tetra-n-butylphosphonium bromide.

The amount of the polymerization catalyst to be added varies depending on the composition of the composition, the mixing ratio, and the polymerization hardening method, and therefore cannot be included, but is usually 100% by mass based on the total composition of the optical material (excluding the polymerization touch). The amount of the medium is 0.0001% by mass to 10% by mass, preferably 0.001% by mass to 5% by mass, more preferably 0.01% by mass to 1% by mass, most preferably 0.01% by mass to 0.5% by mass. When the amount of the polymerization catalyst added is more than 10% by mass, the polymerization may be rapidly performed. In addition, when the amount of the polymerization catalyst added is less than 0.0001% by mass, the composition for an optical material may not be sufficiently cured, and the heat resistance may be poor.

Further, in the production method of the present invention, when an optical material is produced, an additive such as an ultraviolet absorber, a bluing agent or a pigment is added to the composition for an optical material, and of course, the practicality of the obtained optical material can be further improved.

Preferred examples of the ultraviolet absorber include a benzotriazole compound, and a particularly preferred compound is 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole or 5-chloro-2-( 3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-methoxyphenyl)-2H-benzotriazole, 2-(2-hydroxyl -4-ethoxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-butoxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-octyloxybenzene -2H-benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole.

The amount of the ultraviolet absorber to be added is usually 0.01% by mass to 5% by mass based on 100% by mass of the total of the components for the optical material.

When the composition for an optical material is polymerized and cured, the polymerization regulator can be added as needed for the purpose of prolonging the use period or dispersing the polymerization heat. The polymerization regulator can be a halide of Groups 13 to 16 in the long-term periodic table. Among these, a halide of ruthenium, osmium, tin, and iridium is preferred, and a chloride of ruthenium, tin, and osmium having an alkyl group is more preferred. Further preferred compounds are dibutyltin dichloride, butyltin trichloride, dioctyltin dichloride, octyl trichloride, dibutyldichloropurine, butyltrichloropurine, diphenyldichloropurine. Phenyltrichloroanthracene and triphenylphosphonium dichloride, the most preferred compound is dibutyltin dichloride. The polymerization regulator may be used alone or in combination of two or more types.

The amount of the polymerization regulator added is 0.0001 to 5.0% by mass, preferably 0.0005 to 3.0% by mass, and more preferably 0.001 to 2.0% by mass, based on 100% by mass of the total of the optical material composition. When the amount of the polymerization regulator added is less than 0.0001% by mass, a sufficient service life cannot be ensured in the obtained optical material, and if the amount of the polymerization regulator added is more than 5.0% by mass, the composition for an optical material may not be sufficient. When hardened, the heat resistance of the obtained optical material is lowered.

The optical material composition or the polymerizable curable composition thus obtained is molded into a mold or the like and polymerized to form an optical material.

In the injection molding of the composition of the present invention, it is preferred to filter the impurities by a sieve or the like having a pore diameter of about 0.1 to 5 μm to improve the quality of the optical material of the present invention.

The polymerization of the composition of the present invention is usually carried out as follows. That is, the hardening time is usually from 1 to 100 hours, and the hardening temperature is usually from -10 ° C to 140 ° C. The polymerization is carried out by a step of maintaining a specific time at a specific polymerization temperature, a step of raising the temperature of 0.1 ° C to 100 ° C / h, a step of lowering the temperature of 0.1 ° C to 100 ° C / h, or a combination of these steps.

Further, after the hardening is completed, the obtained optical material is subjected to tempering treatment at a temperature of 50 to 150 ° C for about 10 minutes to 5 hours, which is a preferable treatment for removing the skew of the optical material of the present invention. Further, the obtained optical material may be subjected to surface treatment such as dyeing, hard coat layer, impact-resistant layer, reflection prevention, and antifogging property as necessary.

The optical material of the present invention can be suitably used as an optical lens. The optical lens manufactured by using the composition of the present invention is excellent in stability, hue, light resistance, and transparency, and can be used in conventional high-priced high-refractive-index glass lenses such as a telescope, a binocular, and a television projector. In the field, and very useful. It is preferably used in the form of an aspherical lens if necessary. Since the aspherical lens can substantially set the spherical aberration to zero by one lens, the combination of the plurality of spherical lenses can eliminate the spherical aberration and reduce the weight and production cost. Therefore, aspherical lenses are particularly useful as camera lenses among optical lenses.

[Examples]

Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited to the following examples.

1. Preservation stability

The purity of the episulfide compound of the main component in the composition for the optical material at 60 ° C for one week in a nitrogen atmosphere was analyzed by GPC (using the column GPC K-801 manufactured by Showa Denko Co., Ltd., and the RID-10A of Shimadzu Corporation) To detect, the purity is reduced by less than 5% and set to A, and 5% or more of less than 10% is set as B, and 10% or more is set as C. A and B are qualified.

2. Temperature change stability

The solution was stored at -10 ° C for 20 hours under a nitrogen atmosphere, then at 30 ° C for 4 hours, and stored at 30 ° C for 20 hours, and then repeated 10 times at -10 ° C for 4 hours. Thereafter, 40 g of a special grade acetone (99.5% or more, Kanto Chemicals) was added to 10 g of the episulfide compound, and the mixture was thoroughly stirred and allowed to stand for 10 minutes, and the turbidity of the solution was measured using T-2600DA manufactured by Tokyo Electrochrome. When the turbidity is less than 1.0 ppm, it is set to A, 1.0 ppm or more and less than 3.0 ppm is set to B, 3.0 ppm or more and less than 5.0 ppm is set to C, and 5.0 ppm or more is set to D. A, B, and C are qualified.

3. Light resistance evaluation (tone measurement) (1) Determination of initial value

A plate having a thickness of 3.0 mm was produced by the method described in the examples, and a YI value was measured using a color meter JS-555 manufactured by Color technosystem. Set this value to p.

(2) Determination of the change in hue caused by light

After the initial value was measured, the carbon arc combustion light was irradiated for 60 hours, and then the YI value was measured. Set this value to q.

The value of (q-p)/p is calculated. When the value is less than 1.0, it is set to A, 1.0 or more is less than 2.0, and B is set to C. A and B are qualified.

4. Skew

The -4D lens was produced by the method described in the examples, and the skew was evaluated using a lens measuring device (Toshiba skew tester SVP-10-II). No skew is set to A, and skewed is set to B. A is the degree of qualification.

Example 1

To 100 g of bis(β-epithiopropyl) sulfide (hereinafter referred to as "compound a") and 200 ml of toluene as a compound represented by the above formula (2), 150 g of acetic acid was added, and the mixture was reacted at 40 ° C for 10 hours. After the completion of the reaction, water is added and washed, and the obtained organic layer is further washed with water three times, and the solvent is distilled off, followed by purification by a column to obtain a compound represented by the following formula (hereinafter referred to as the compound represented by the above formula (1) (hereinafter, It is "compound b") 12g.

¹ H-NMR (CDCl ₃ ): 1.5 ppm (1H), 2.0 ppm (3H), 2.2 ppm (2H), 2.5 ppm (1H), 2.7-2.8 ppm (4H), 3.4 ppm (1H), 4.3 ppm ( 2H)

¹³ C-NMR (CDCl ₃ ): 17 ppm, 25 ppm, 33 ppm, 37 ppm (2H), 44 ppm, 74 ppm, 171 ppm

Example 2

To 100 g of bis(β-epithiopropyl) disulfide (hereinafter referred to as "compound c") of the compound represented by the above formula (2) and 200 ml of toluene, acetic acid 150 was added, and the mixture was reacted at 40 ° C for 10 hours. After the completion of the reaction, water is added and washed, and the obtained organic layer is further washed with water three times, and the solvent is distilled off, followed by purification by a column to obtain a compound represented by the following formula (hereinafter referred to as the compound represented by the above formula (1) (hereinafter, It is "compound d") 10g.

¹ H-NMR (CDCl ₃ ): 1.5 ppm (1H), 2.0 ppm (3H), 2.2 ppm (2H), 2.5 ppm (1H), 2.8-3.0 ppm (4H), 3.4 ppm (1H), 4.3 ppm ( 2H)

¹³ C-NMR (CDCl ₃ ): 17 ppm, 24 ppm, 32 ppm, 35 ppm, 40 ppm, 46 ppm, 74 ppm, 171 ppm

Example 3~9

To the compound a (the compound of the formula (2)), the compound b (the compound of the formula (1)) shown in Table 1 was added, and the storage stability and the temperature change stability were evaluated. The results are shown in Table 1.

Example 10~16

The compound d (the compound of the formula (1)) shown in Table 1 was added to the compound c (the compound of the formula (2)), and the storage stability and the temperature change stability were evaluated. The results are shown in Table 1.

Comparative example 1

Only the stability of the compound a (the compound of the formula (2)) was evaluated. The results are shown in Table 1.

Comparative example 2

Only the stability of the compound c (the compound of the formula (2)) was evaluated. The results are shown in Table 1.

[Table 1]

From the results of Table 1, it was found that the compound represented by the formula (2) (compound b or d) was added to the compound represented by the formula (2) (compound b or d), and the storage stability was excellent.

Examples 17~23

An optical material group for mixing the compound b (the compound of the formula (1)) in an amount shown in Table 2 with respect to the compound a (the compound of the formula (2)) To the total amount of the product, 1.0% by mass of 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole as a UV absorber, tetra-n-butyl bromide as a polymerization catalyst After the hydrazine was 0.05% by mass, it was thoroughly mixed at 20 ° C. Thereafter, the mixture was evacuated at a vacuum of 1.3 kPa, and injected into a mold composed of two glass plates and a tape (for a 3.0 mm thick plate and a -4D lens), and kept at 30 ° C for 10 hours to 10 The time of the hour was raised to 100 ° C at a constant rate, and finally maintained at 100 ° C for 1 hour to cause polymerization hardening. After cooling, the mold was released from the mold, and tempered at 110 ° C for 60 minutes to obtain a molded plate (a 3.0 mm thick plate and a -4D lens). The light resistance evaluation (tone measurement) of the flat plate was shown in Table 2 together with the skew result of the -4D lens.

Comparative example 3

To the compound a (the compound of the formula (2)), 1.0% by mass of 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole as a UV absorber was added as a polymerization catalyst. After tetra-n-butylphosphonium bromide was 0.05% by mass, it was thoroughly mixed at 20 ° C. Thereafter, the mixture was evacuated at a vacuum of 1.3 kPa, and injected into a mold composed of two glass plates and a tape (for a 3.0 mm thick plate and a -4D lens), and kept at 30 ° C for 10 hours to 10 The time of the hour was raised to 100 ° C at a constant rate, and finally maintained at 100 ° C for 1 hour to cause polymerization hardening. After cooling, the mold was released from the mold, and tempered at 110 ° C for 60 minutes to obtain a molded plate (a 3.0 mm thick plate and a -4D lens). The light resistance evaluation of the flat plate was shown in Table 2 together with the skewing result of the (toner measurement)-4D lens.

Example 24~30

The composition for an optical material of the compound d (the compound of the formula (1)) in an amount shown in Table 2 is mixed with the compound c (the compound of the formula (2)), and 2-(2-hydroxyl group) as an ultraviolet absorber is added. -5-t-octylphenyl)-2H-benzotriazole 1.0% by mass, and 0.5% by mass of N,N-dimethylcyclohexylamine as a polymerization catalyst, and sufficiently mixed at 20 ° C. Thereafter, the mixture was evacuated at a vacuum of 1.3 kPa, and injected into a mold composed of two glass plates and a tape (for a 3.0 mm thick plate and a -4D lens), and kept at 30 ° C for 10 hours to 10 The time of the hour was raised to 100 ° C at a constant rate, and finally maintained at 100 ° C for 1 hour to cause polymerization hardening. After cooling, the mold was released from the mold, and tempered at 110 ° C for 60 minutes to obtain a molded plate (a 3.0 mm thick plate and a -4D lens). The light resistance evaluation (tone measurement) of the flat plate was shown in Table 2 together with the skew result of the -4D lens.

Comparative example 4

To the compound c (the compound of the formula (2)), 1.0% by mass of 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole as a UV absorber was added as a polymerization catalyst. After adding 0.5% by mass of N,N-dimethylcyclohexylamine, it was thoroughly mixed at 20 ° C. Thereafter, the mixture was evacuated at a vacuum of 1.3 kPa, and injected into a mold composed of two glass plates and a tape (for a 3.0 mm thick plate and a -4D lens), and kept at 30 ° C for 10 hours to 10 Hour time to increase the temperature to 100 at a certain speed °C, finally held at 100 ° C for 1 hour, allowing polymerization to harden. After cooling, the mold was released from the mold, and tempered at 110 ° C for 60 minutes to obtain a molded plate (a 3.0 mm thick plate and a -4D lens). The evaluation of the light resistance of the flat plate and the results of the skew of the (toner measurement)-4D lens are shown in Table 2.

From the result of Table 2, it was found that the compound (compound b or d) represented by the formula (1) was added to the compound (compound a or c) represented by the formula (2), and the light resistance was excellent.

Claims (10)

An episulfide compound represented by the following formula (1), (where m represents an integer from 0 to 4, and n represents an integer from 0 to 2). A composition for an optical material comprising the episulfide compound of claim 1 and a polymerizable compound other than the compound. The composition for an optical material according to claim 2, wherein the content of the episulfide compound is 0.001 to 5.0% by mass. The composition for an optical material according to claim 2, wherein the polymerizable compound is contained in an amount of from 95.0 to 99.999% by mass. The composition for an optical material according to any one of claims 2 to 4, wherein the compound represented by the following formula (2) is contained as the polymerizable compound, (where m represents an integer from 0 to 4, and n represents an integer from 0 to 2). The composition for an optical material according to claim 5, which contains 40 to 99.999 mass% of the compound represented by the above formula (2). A polymeric hardenable composition comprising the requirements of claims 2 to 6 The composition for an optical material according to any one of the above, and the polymerization catalyst, wherein the total amount of the polymerization catalyst is 0.0001% by mass to 10% by mass based on the total amount of the composition for the optical material. An optical material which is a composition for an optical material according to any one of claims 2 to 6 or a polymeric hardenable composition according to claim 7. An optical lens comprising the optical material of claim 8. A method for producing an optical material, which comprises adding a polymerization catalyst in an amount of 0.0001% by mass to 10% by mass based on the total amount of the composition for an optical material according to any one of claims 2 to 6, and then performing polymerization hardening. step.